Process for breaking petroleum emulsions



I Patented Feb. 2%, 1944 PROCESS FOR BREAKING PETROLEUM EMULSIONS MelvinDe Groote, University City, Mo., assignor to Petrolite Corporation,Ltd., Wilmington, Del., a corporation of Delaware No Drawing.Application September 8, 1941,

. Serial No. 410,084

16 Claims. (Cl. 252-341) This invention relates to a process forbreaking petroleum emulsions, my present application being acontinuation, in part, of my co-pending application, Serial No. 360,804,filed ()ctober 11,

ture, as a condensation product. Attention is directed to the followingtwo sentences which appear on pages 21 and 22 of the specification ofsaid aforementioned co-pending application, Serial No. 360,804, filedOctober 11,1940:

It has been previously pointed out that a large variety of the materialsherein described represent surf ace-active materials or morespecifically, cation-active materials. Therisawidpgarity of uses forsuch surface-acting materials. Also The products may be used asdemulsifiers in the manner that such materials are most widely used inthe production of crude oil or removal of salt in refinery practice.

The subsequent subject-matter of the instant specification issubstantially a verbatim copy of the subject-matter appearing in theaforementioned co-pending application, except that there is eliminatedsuch data as is concerned primarily with acidization of calcareousstnucture, and reference to the matter contemplated is as a con-.densation product, chemical compound, or the like, rather than specificreference to it as an emulsion-preventing agent.

The condensation product or chemical compound used as the demulsifyingagent in my herein disclosed process for breaklngpetroleum emulsions ofthe water-in-oil type, is obtained by reaction between a highermolecular weight monocarboxy acid or its functional equivalent, and apolymerized .polyamine derived from a hydroxylated polyamine containingat least one nitrogen atom not directly linked to a hydroxy hydrocarbonradical, and preferably, at least two amino nitrogen atoms not directlylinked to a hydroxy hydrocarbon radical. Such reactants are mixedtogether so that there is at least one mole of the high molal carboxyacid for each mole of polymerized hydroxylated polyamine; .and there maybe several moles of such high molal carboxy acid combined with each moleof the polymerized hydroxylated amine. Such condensation is effected bythe action of the heat generally at a temperature above 100 C., and maybe conducted at a temperature as high as 300 C. Generally speaking, therange of ISO-175 C. represents an optimum temperature. Preferably,condensation is conducted by first polymerizing such hydroxylated aminesand then condensing the polymerized hydroxylated polyamine with theselected alcohol. Polymerization catalysts consist oi materials of thekind commonly employed to polymerize hydroxylatedmcncamine, such astriethanolamine. They include materials such as caustic soda, causticpotash, high molal amines, soaps, sodium glycerate, sodium methylate,sodium ethylate, and the like. The amounts used vary from 1% toapproximately 0.1%, or even less. Polymerization is generally conductedat a temperature range of approximately 225-275 C. Constant stirring isdesirable during polymerization, and condensation. Such condensationproducts are usually cation-active materials.

The detailed composition of the products obtained is not known;although; in a'general way, ester linkages must be involved.

As indicated, an amine may act as acatalyst; or, stated anotherway, thehydroxylated amine of the kind employed as a reactant in the productionof the emulsion-preventing agent or condensation product, may act as itsown polymerization catalyst. For instance, in condensation productExamples 1-8, inclusive, as described subsequently, the added catalystmay be eliminated or reduced, with probable increased time ofcondensation being required. Thus, in the hereto appended claims,reference to a catalyst is intended to include the amine itself, as wellas an added catalyst, if employed. For this reason many of theproperties of the materials are unpredictable.

It is surprising to find that such materials are stable for an extendedperiod of time in half-concentrated hydrochloric acid, or other similarmineral acids. It 'is likewise remarkable to note .that such solutionsin acid, and particularly in detailed probable structure for suchcompounds which would account for their resistance to decomposition instrong acid solution.

In practising my present process for breaking petroleum emulsions of thewater-in-oil type, a treating agent or demulsifier, consisting of amaterial of the kind above referred to is brought into contact with orcaused to act upon the emulsion to be treated, in any of the variousways, or by any of the various apparatus now generally used to resolveor break petroleum emulsions with a chemical reagent, the aboveprocedure being used alone or in combination with other demulsifyingprocedure, such as the electrical dehydration process.

Materials of the kind herein contemplated are derived from variousreactants. One class of reactants consists of higher molecular weightcarboxy acids, and particularly, monocarboxy acids or their functionalequivalents, such as the acyl' halide, ester, amide, etc. The expressionhigher molecular weight carboxy acids" is an expression frequentlyemployed to refer to certain organic acids, particularly monocarboxyacids, having and carnauba wax. Such acids include carnaubic acid,carotic acid, lacceric acid, montanic acid, psyllastearic acid, etc. Assuggested, one may also employ higher molecular weight carboxylic acidsderived, by oxidation and other methods, from paraflin wax, petroleumand similar hydrocarbons; resinic and, hydroabietic acid; aralkyl andaromatic acids, such as benzoic acid, Twitchell fatty acids, naphthoicacid, carboxydiphenyl pyridine carboxylic acid, hydroxybenzoic acid, andthe like. Other suitable acids include phenylstearic acid,benzoylnonylic acid, cetyloxyacetic acid, chlorstearic acid, fencholicacid, cetyloxybutyric acid, etc.

Insofar that the fatty acids are preferably employed as a source of theacyl radical, obviously one need not use the fatty acids, themselves,but.

may employ any obvious functional equivalent, such as an ester,anhydride, amide, acyl halide, etc. It is understood that in the heretoappended claims reference to formation of a condensation product beingderived from an acid is intended to include such obvious functionalequivalents. In such instances, instead of elimination of more than 6carbon atoms, and generally less water, one may have some othercompound, such than 40 carbon atoms. The commonest examples as-ammoniaor hydrochloric acid, eliminated.

tion of petroleum. As will be subsequently ili ii cated, there are otheracids which have somewhat similar characteristics and are derived fromsomewhat difierent sources and are difierent in structure, but can beincluded in the broad generic term previously indicated.

Among sources of such acids may be mentioned straight chain and branchedchain, saturated and unsaturated, carboxylic, aliphatic, alicyclic,fatty, aromatic, hydroaromatic, and aralkyl acids, including caprylicacid, heptylic acid, caproic acid, capric acid, pime1ic acid, sebacicacid, erucic acid, s aturated anduunsaturatedg higher molecular weightaliphatic acids, such as the higher fatty acids containing at least 8carbon atoms, and including, in addition to those mentioned, melissicacid, stearic acid, oleic acid, ricinoleic acid, diricinoleic acid,triricinoleic acid, polyricinoleic acid,-ricinostearolic acid,ricinoleyl lactic acid, acetylricinoleic acid, 'chloracetylricinoleicacid, linoleic acid, linolenic acid, lauric acid, myristic acid,undecylenlc acid, palmitic acid, mixtures of any two or more of theabove mentioned acids or other acids, mixed higher fatty acids derivedfrom animal or vegetable sources, for example, lard, cocoanut oil,rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, cornoil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil,castor oil, seal oils, whale oil, shark oil, and other fish oils,teaseed oil, partially or completely hydrogenated animal and vegetableoils, such as those mentioned; hydroxy and alpha-hydroxy highercarboxylic aliphatic and fatty acids, such as dihydroxystearic acid,dihydroxy palmitic acid, dihydroxybehenic acid, alpha-hydroxy capricacid, alpha-hydroxy lauric acid, alphahydroxy myristic acid,alphahydroxy cocoanut oil mixed fatty acids, alphahydroxy margaric acid,alphahydroxy arachidic acid, and the like; fatty and similar acidsderived from various waxes, such as beeswax,

As hasbeenpreviously indicated, the second class of reactants isobtained by polymerization of certain hydroxylated polyamines.

Such hydroxylated polyamines characterized by the presence of at leastone amino nitrogen atom not directly attached to a hydroxy hydrocarbonradical, are well known compounds. They may be obtained in various ways.The commonest procedure is to treat a polyamine with an alkylene oxideor its equivalent, such as ethylene oxide, propylene oxide, glycidol, orthe like. The commoner polyamines which can be so treated with anoxy-alkylating agent include the following: ethylene diamine; diethylenetriamine; triethylene tetramine; tetraethylene pentamine; pentaethylenehexamine; propylene diamine; dipropylene triamine; tripropylenetetramine; tetrapropylene pentamine; pentapropylene hexamine, etc. Insome instances such amines may be treated with an alkylating agent orthe like so as to introduce an alkyl, aralkyl, or alicyclic radical intothe compound as a substitute for an amino hydrogen atom. For instance,one may obtain diethyl tetraethylene pentamine in the conventionalmanner, using ethyl iodide or the like as an alkylating agent.

In any event, having selected a suitable polyamine, the product is thentreated with any acceptable oxy-alkylating agent, such as ethyleneoxide, propylene oxide, and the like. In view of the lower cost ofethylene oxide, and in view of the greater activity, it is mostfrequently employed. For instance, ethylene diamine can be treated withone mole of ethylene oxide to produce hydroxyethyl ethylene diamine.Diethylene triamine can be treated with three moles of ethylene oxide soas to yield triethanol" diethylene triamine. Triethylene tetramine canbe treated with four moles of ethylene oxide to yield tetraethanoltriethylene tetramine. Similarly, one can obtain tetraethanoltetraethylene pentamine, or tetraethanol pentaethylene' hexamine. Onecan employ propylene oxide or glycidol to give similar products. In viewof the fact that the most inexpensive polyamine now available istetraethylene pentamine, I prefer to treat tetraethylene pentamine withthree moles, four moles, or five moles of ethylene oxide to give thecorsp ac t montan Japan cocce in, 7 responding triethanol, tetraethanol,and penal-- ethanol derivatives and to employ such derivatives.

In the manufacture of the compound or product employed as thedemulsifying agent of my process, it is sometimes desirable to add apolyhydric alcohol, such as glycerol, ethylene glycol, diethyleneglycol, diglycerol, propylene glycol, or the like. The eifect of addingsuch polyhydric alcohol is essentially the same eifect as would beobtained by treating the high molal alcohol with an alkylene oxide, suchas ethylene oxide, propylene oxide, glycidol, or the like, or treatingthe unpolymerized hydroxylated amine in a similar manner, or treatingthe polymerized hydroxylated amine in a kindred fashion.

In view of the numerous reactants which have been indicated, it isobvious that one can obtain a variety of condensation products oremulsionpreventing reagents. If a compound or emulsionpreventing agentis not soluble enough, its solubility, or the solubility of its salt,can be increased in various manners, for instance:

(a) Employ a monocarboxy acid having a lower molecular weight;

(b) Use fewer moles of acid per mole of original unpolymerizedpolyamine;

Select as a raw material an amine having a. greater 'number of aminonitrogen atoms;

(d) Select as a raw material an amine having a greater number of hydroxyhydrocarbon radicals;

(6) Select as an amine a compound having both an increased number ofnitrogen atoms and an increased number of hydroxy hydrocarbon radicals;

(I) Add a polyhydric alcohol, such as glycerol, at some selected stagesubsequently indicated; and

(g) Vary the degree of polymerization of the hydroxylated amine in themanner subsequently indicated.

Inversely, it will sometimes happen that the condensation product oremulsion-preventing agent is too soluble; or, to state the matteranother way, it does not possess sufiicient surface activity for thepurpose intended. In such instances it may be desirable to decrease thehydrophile properties. It is unnecessary to remark that this requiresonly a reversal of one or more of the procedures previously enumerated.It is believed that in view of what has been said, the compounds of thekind contemplated can be prepared without further directions orillustrations. However, for the purpose of indicating the preferabletype of condensation product or emulsion-preventing agent, attention isdirected to the following examples:

Polymerzzed hydroxylated polyamine-Example 1 Triethylene tetramine istreated with four moles of ethylene oxide to produce tetraethanoltriethylene tetramine. Approximately threefourths of a percent ofcaustic soda is added to this material by weight and the hydroxylatedamine is heated for approximately two to four hours at about 245-260" C.The mass is stirred constantly and any distillate is condensed andreserved for re-use after an intermediate rerunning step. Aspolymerization takes place, as indicated by elimination of water andincrease in viscosity of the residual mass, cryoscopic molecular weightdeterminations are made on the polyamine or a suitable salt, such as theacetate, or the like, and polymerization is stopped when such molecularweight determinations indicate that the material based on average valuesis largely dimeric.

Polymerized hydrozylated polyamine-Example 2 The same procedure isemployed as in the previous example, except that heating is conductedfor approximately 1-3 hours longer.

Tests are made in the same manner as previously indicated, andpolymerization is stopped when determinations indicate that the averagemolecular weight is equivalent to a trimeric product. 7

Polymerized hydroxylated polyamine-Example 3 erage molecular weightequal to or exceeding that I of a tetramer.

Polymerized hydrozcylated polyamine-Example 4 The preceding examples arerepeated, adding one mole of glycerol for each mole of hydroxylatedamine employed.

Polymerized hydroxylated polyamine--E:cample 0 Examples 1-3, inclusive,are repeated, adding two moles of glycerol for each mole of hydroxylatedpolyamine employed.

Polymerized hydroxylated polyamz'ne-Emample 6 Tetraethanol pentaethylenehexamine is substituted for tetraethanol triethylene tetramine inExamples 1-5.

Polymerieedhydroxylated polyamine-Example 7 Tetraethanol tetraethylenepentamine is substituted for tetraethanol pentaethylene hexamine in thepreceding example.

Polymerized hydrozylated polyamine-Example 8 Pent hanol tetraethylenepentamine is substituted =.cr tetraethanol tetraethylene pentamine inthe preceding example.

Polymerized hydroxylated polyamineE:cample 9 Hexa-ethanoltetraethylenepentamin is substituted for pentaethanol tetraethylene pentamine in theprevious example.

The mixture of such reactants, i. e., the polymerized hydroxylated amineand the high molal carboxy acid or its equivalent, are prepared in suchratio that there is present at least one mole of the high molal fattyacid or its equivalent for each mole of polymerized amine. My preferenceis to use a dimeric, trimeric, or tetrameric form of the polymerizedhydroxylated amine. My preference also is to use a fatty acid, ratherthan any other type of monocarboxy acid, and particularly to employunsaturated fatty acids, such as soyabean fatty acids, teaseed oil fattyacids, corn oil fatty acids, and the like. The most desirableunsaturated fatty acid appears to be ricinoleic acid. It is used, ifdesired, in a more available form, to wit, the glyceride. In otherwords, in subsequent Example 1 and succeeding examples, it is reallypreferable to substitute one pound mole of triricinolein (castor oil)for three pound moles of ricinoleic acid.

The temperature of condensation has previously been indicated. In ageneral way, it is above i'erred range indicated in succeeding examplesis 150-175 C., in many instances very valuable reagents are obtained byusing a, considerably higher temperature, to wit, 250-300" C.

Condensation product-Example 1 A mixture is prepared, using one poundmole each or the following: ricinoleic acid and a material of the kindexemplified by polymerized hydroxylated polyamine, Example 1. Theproducts are mixed and stirred constantly, holding the temperature atapproximately 150-175 C., until no unreacted high molal acid remains.The bulk of such high molal acid generally disappears within two tothree hours; but sometimes it is necessary to heat from 4 to 6, or even10, hours to obtain substantially complete reaction. The finalcompletion of reaction is indicated in various ways, and usually by thefact that the product gives a clear solution in dilute acetic acid.

Condensation product-Example 2 One pound mole of ricinoleic acid inExample 1 above is replaced by twopound moles.

Condensation product-Example 3 Oleic acid is used instead of ricinoleicacid in Examples 1 and 2, preceding.

Condensation productExample 4 Abietic acid is used instead of ricinoleicacid in Examples 1 and 2, preceding.

Condensation product-Example 5 Naphthenic acid is used instead ofricinoleic acid in Examples 1 and 2, preceding.

Condensation product-Example 6 The examples of the type previouslyindicated are repeated, with the addition of one pound mole of glycerolfor each pound mole of the high molal alcohol.

Condensation productEa:ample 7 Example 6 is repeated, usin two poundmoles of glycerol in each instance instead of one pound Examples 1-7,preceding, are repeated, using polymerized hydroxylated polyamines,Examples 2-9, instead of Example 1, as in the previous examples.

In the hereto appended claims, reference to the use of the condensationproduct is intended to include the baseiorm, i. e., the chemicalcombination of water, and also the salt form such as the lactate,acetate, citrate, or the like.

Having thus described my invention, what I claim as new and desire tosecure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsiiyingagent comprising the condensation product derived from one mole of apolymerized amine obtained by heat polymerization in presence of acatalyst, from a hydroxylated polyalkylene amine containing at least oneamino nitrogen atom not directly linked to a hydroxy-hydrocarbonradical, and at leastlone mole of a higher molecular weight monocarboxyacid containing at least 8 carbon atoms. 7

2. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising the condensation product derived irom one mole of apolymerized amine obtained by heat polymerization in presence of acatalyst, from a hydroxylated polyalkylene amine containing at least oneamino nitrogen atom not directly linked to a hydroxy-hydrocarbonradical, and at least one mole of a detergent-forming acid containing atleast 8 carbon atoms. a

3. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising the condensation product derived from one mole of apolymerized amine obtained by heat polymerization in presence of acatalyst, from a hydroxylated polyalkylene amine containing at least oneamino nitrogen atom not directly linked to a hydroxy-hydrocarbonradical, and at least one mole of a fatty acid containing at least 8carbon atoms.

4. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising the condensation product derived from one mole of apolymerized amine obtained by heat polymerization in presence of acatalyst, from a hydroxylated polyalkylene amine containing at least oneamino nitrogen atom not directly linked to a hydroxy-hydrocarbonradical, and at least one mole of an unsaturated fatty acid containingat least 8 carbon atoms.

5. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising the condensation product derived from one mole of apolymerized amine obtained by heat polymerization in presence of acatalyst, from a hydroxylated polyalkylene amine containing at least twoamino nitrogen atoms not directly linked to a hydroxy-hydrocarbonradical, and at least one mole of an unsaturated fatty acid containingat least 8 carbon atoms.

6. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising the condensation product. derived from one mole of apolymerized amine obtained by heat polymerization in presence of acatalyst, from a hydroxylated polyethylene amine containingat least twoamino nitrogen atoms not directly linked to a hydroxy-hydrocarbonradical, and at least one mole of an unsaturated fatty acid containingat least 8 carbon atoms.

7. A process ion-breaking petroleum emulsions of the water-in oil type,characterized by subjecting the filing agentcomprising the condensationproduc derived from one mole of a polymerized amine" obtained by heatpolymerization in presence eniulsion to the action of a demulsij/ atedfatty acid containing at least 8 carbon toms. I 9. A process forbreaking petroleum emulsions f the water-in-oil type, characterized bysub acting the emulsion to the action of a demulsiying agent comprisingthe condensation product .erived from one mole of a polymerized aminebtained by heat polymerization in presence of catalyst, from ahydroxylated polyalkylene mine containing at least one amino nitrogen.tom not directly linked to a hydroxy-hydrocaron radical, at least onemole of a higher molecuar weight monocarboxy acid containing at leastcarbon atoms, and at least one mole of a polyiydric alcohol.

10. A process for breaking petroleum emulsions f the water-in-oil type,characterized by subecting the emulsion to the action of a demulsiyingagent comprising the condensation product lerived from one mole of apolymerized amine ob-- ained by heat polymerization in presence of a:atalyst, from a hydroxylated polyalkylene amine :ontaining at least'oneamino nitrogen atom not lirectly linked to a hydroxy-hydrocarbonradical, it least one mole of a detergent-forming acid conaining atleast 8 carbon atoms, and at least one nole of a polyhydric alcohol.

11. A process for breaking petroleum emulsions )f the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingigent comprising the condensation product de-' rived from one mole of apolymerized amine ob- ;ained by heat polymerization in presence of a:atalyst, from a, hydroxylated polyalkylene amine :ontaining at leastone amino nitrogen atom not iirectly linked to a hydroxy-hydrocarbonradi- :al, at least one mole of a fatty acid containing at least 8carbon atoms, and at least one mole of a polyhydric alcohol.

12. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subi ecting the emulsion to the action of ademulsifying agent comprising the condensation product derived from onemole of a polymerized amine obtained by heat polymerization in presenceof a catalyst, from a hydroxylated polyalkylene amine containing atleast one amino nitrogen atom notdirectly linked to ahydroxy-hydrocarbon radical,

at least one mole of an unsaturated fatty aci containing at least 8carbon atoms, and atleast one mole of a polyhydric alcohol.

13. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising the condensation product derived from one mole of apolymerized amine obtained by heat polymerization in presence of acatalyst, from a hydroxylated polyalkylene amine containing at least twoamino nitrogen atoms not directly linked to a hydroxy-hydrocarbonradical, at least-one mole of an unsaturated fatty acid containing atleast 8 carbon atoms, and at least 15' one mole of a polyhydric alcohol.

14. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsifyingagent comprising the condensation product derived from one mole of apolymerized amine obtained by heat polymerization in presence of acatalyst, from-a hydroxylated polyethylene amine containing at least twoamino nitrogen atoms not directly linked to a hydroxy-hydrocarbonradical, at least one mole of an unsaturate fatty acid containing atleast 8 carbon atoms, and at least one mole of a polyhydric alcohol,

15. A process for breaking petroleum emulsions of the water-in-oil typcharacterized by subjecting the emulsion to the action of a demulsiiyingagent comprising the condensation product derived from one mole of apolymerized amine obtained by heat polymerization in presence of acatalyst, from tetraethanol tetraethylene pentamine. at least one moleof an unsaturated fatty acid containing at least 8 carbon atoms, and atleast one mole of apolyhydric alcohol.

16. A process for breaking petroleum emulsions of the water-in-oil type,characterized by subjecting the emulsion to the action of a demulsityingagent comprising the condensation product derived from one mole ofa'polymerized amine obtained by heat polymerization in presence of acatalyst, from'pentaethanol tetraethylene pentamine, at least one moleof an unsaturated fatty acid containing at least 8 carbon atoms, and atleast one mole of a polyhydric alcohol.

' MELVIN DE GROOTE.

